Insecticide



Patented Aug. 20, 194

CaliL,

'- UNITED STATES PATEN o 2.40am

INSECTICIDE James W. llansen and Carroll 0.

asslgnors to California Spray-Chemical oFFics QassiL Berkeley.

Corporation, Richmond, Calif a corporation of Delaware No Drawing. Application June 21, 4945, Serial No. 601,916

12 Claims. (1167-33) This invention relates to compositionswhich are highly effective in the control'of may insect pests, and which contain as an active toxic ingredient a synthetic organic compound which we have discovered, namely, cyclopropyl-furyl prov penone.

As is well known, substances which possess the pyrethrum has the property of producing a high I degree of knock-down, but many of the insects so immobilized ultimately recover. We have found that cyclopropyl furyl propenone, even when used in low concentration, combines to an outstanding degree the properties of high knockdown and high mortality. At the same time this substance can be synthesized without difficulty; and it is free from objectionable odor. Furthermore, whenused in amounts adequate to afford satisfactory pest control, it has noundesirable effect on fabrics or furniture, and produces no cations of insecticide, with corresponding wastage.

These disadvantages are in substantial degree overcome by the use of cyclopropyl furl/l propenone. Due to its relatively high vapor pressure and the toxicityof its vapors its lethal effectiveness is not limited to'direct contact, but tends to permeate adjacent cracks, webs, and other sheltered places, so that when dispersed inthe form of a spray or a dust it acts both as a contact poison and as a fumlgant.

Moreover, the toxicity of the vapor of cyclo-' propyl furyl propenone is such that it may be used simply as a fumigant against many insect pests including'the clothes moth. Evaporation at room temperature is sufllciently rapid so that no heating is needed for most fumigations. 1

The compound which we have discovered to possess these valuable propertieswhich make it irritation or symptoms of toxicity in contact with warm' blooded animals. 7

iThe compound of our invention possesses, in addition to the power to paralyze and kill many insects on directcontact, thepower to kill by means of the toxicity of its vapor. This surprising combination of properties adds .to the effectiveness of the, insecticidal compositions described herein containing cyclopropyl furyl propenone.

I I It'is well known that the contact insecticides in common use are effective only insofar as the solid or liquid phase of the material can be applied to the body of the insect. It is,extremely dimcult and usually impossible to reach all of the insects in an infested area with a'spray or dust. Some of the insects will be in protected locations such as crevices, leaf curls, etc., and will escape. fact necessitates both heavy and repeated appli- .This

outstanding for use as a toxic ingredient of insecticides is chemically described as "l-cyclopropyl, 3(2-furyl), Z-propen-l-one. It is for convenience referred to herein as cyclopropyl furyl propenone." Its structural formula is as follows:

. CHI-CH cHr-en-c-cn=cnn One method of preparing this compound is as follows: Cyclopropyl methyl ketone and furfural in approximately equimolar ratio are a itated in the presence of an aqueous alkaline solution for several hours at normal atmospheric temperature. Following this period of agitation the reaction mix is allowed to settle. Cyclopropyl furyl propenone settles readily to the bottom of the vessel either in the form of yellow crystals or,

in some cases, possibly due to the absence of seed crystals, in the form of an oily liquid. The product is segregated, by decantation, for example, and is washed with water or with dilutemi'neral acid. It may be further purified by simple steam distillation or, if greater purity is required, by

. vacuum distillationor by recrystallization from a solvent such as petroleum ether.

The pure substance, cyclopropyl furyl propenone, is, at normal atmospheric temperature, a colorless crystalline solid. The crystals are reg ular, 'rhombic, tabular in form, and exhibit parallel extinction. Crystallization does-not take place readily except in the presence of;at least a minute seed crystal of the substance, and, therefore, if reasonable precautions are taken,

tures many degrees below its melting point. In liquid form, cyclopropyl furyl propenone is a light This substance has the following properties:

This substance is soluble in such organic solit may, be preserved as a liquid even at temperastraw color and has a distinctive, agreeable odor.

vents asacetone, ether, petroleum ether and furfural. It is sufllciently' soluble in petroleum oil fractions such as kerosene and spray oils to permit its efiective use as an insecticide in such carriers.

Cyclopropyl furyl propenoneis somewhat unstable in the pure state even when kept in the dark and gradually changes from colorless to slightly yellow. The'technical material as obtained without recrystallization will, on standing,

change in color from light amber to dark yellow or dark red. -This change reaches equilibrium after a short time, and aflects only one to five per cent of the material. when dissolved in pee troleum oil, the stability of cyclopropyl furyl propenone is improved even in -the presence of strong sunlight. This slight instability is without apparent eifect on the insecticidal value of the compound. Consequently, it is usually not necessary to resort to recrystallization or vacuum distillation when preparing the product for insecticidal compounding.

Cyclopropyl furyl propenone possesses insecticidal propertiesto a high degree. Since it is extremely toxic to houseflies and mosquitoes it is very valuable for use in a 'household spray, i. e.,' as an ingredient in compositions adapted to be used as a pace spray. For-thisp rp se it is desirable to incorporate it with a light well-reiined petroleum distillate of the kerosene type suitable for dispersion by, means of a spray gun.

' An example of a suitable sprayable material for.

such use is 2% to 5% by weight of cyclopropyl 'furyl' propenone dissolved in 98% to 95% by weightv of light petroleum oil. A typical petroleum oil suitable for use in such spray solution is a-reflnedterosene type fraction having the- .4 likewise show for comparison results obtained by the use .of aspray containing pyrethrum. The

composition used for these tests consisted of small percentages of the toxic ingredient in solution in light petroleum (kerosene)' oil of about 0.8018 specific gravity and unsulfonated residue of 95. The same oil, the same test apparatus and procedure and the same strain of houseflies (identically reared under laboratory conditions) were usedin all tests. All tests werereplicated several times. The results were obtained by the Hosklns technique in a standard "Hoskins chamber (described in Chemical Control of Insects," edited by Campbell and Molten, 1943, at page- 130),-us ing 4 ml. of spray solution in each test.

1 Commercial 20 to 1" extract containing 2.4% pyrethrins.

' The eflicacy of sprays of light oil containing cyclopropyl furyi propenone against other insects is further shown by the'following results .of carefully ccntrolledtests:

ff on de v P propy ury ercen propenone in light g g Insect mortality spray oil 1 7.5.. 1. 2 German cockroach. 100 0 Blank ODJYL... 1.2 d0 n 0 7.5 l. 2 European earwlg. 100 3.76 v 1. 2 25 Blank (oilonly).- 1.2 do 0 5 0. 8 Potato tuber moth larvae 65 Blank (oil only) 0.8 .-do i0 C yclopropyl furyl propenone has a distinctive but pleasant odor, and therefore its use in house- .hold sprays does not require the addition of a perfume or masking odor, as is the case with ordiciently'pleasantso that it masks the odor of the following qualities:

Specific gravity 0.8018

Sayboit Universal viscosity PL. 32 to 100 Unsulfonated rosidue 9'5 ABTM distillation: Initial s- 1L. 840- End point .3 r'

This composition produces highly efiicien-t re.-

,sults, i'. e., rapid knock-down and high mortality,

when atomized into a room without further dilution. At the same time it does not damage walls,

, v to the skin and'allowed to remain vfor fifteen l minutescaused no discomfort and produced no redness or other evidence of irritation or stain.

The eflectiveness of cyclopropyl 'furyl propenone when used as a spray in oil against house- 'ilies is shown by the following test results, which kerosene. I

Cyclopropyl furylvpropenone maybe advantageously used as an aerosol, due to its property of effective knock-down, as well as its solubility in available oils, alcohols and ethers. This use is brought about by dissolving it in a solvent which is substantially immediately volatile at average atmospheric conditions, the solution being kept in a tight container under sufllcient pressure to maintain the solvent in liquid form until desired for use. 7

Although cyclopropyl furyl propenone may be effectively used in combatting insect pests by bringing it into contact with the insects by some of tests carried out under carefully controlled laboratory conditions. A quantity. of crystalline cyclopropyl furyl propenone (500 mg.) was placed in a loosely woven cloth container which was in-.-

'serted in the lid of a wide-mouth one-gallon glass jar and test insects were placed at the bottom of the jar. Evaporation under normal atmospheric conditions was allowed to continue for two hours, following which the lid was removed, the jar aired out and covered with a clean cloth. The following results were observed:

Per cent kill (24 hours) Rose ap 70 Bean weevil 80 Clothes moth 100 Mediterranean flour moth 100 Confused flour beetle 10 Due to its effectiveness as a fumigant against various insect pests, and its pleasant odor, cyclopropyl furyl propenone is well adapted for the periodic control of such insects as moths and fleas in living and storage apartments, for easy and effective use in greenhouses, and for the 2 fumigation f seed and grain.

Another field of use for the'oompound describe is in horticulture. For such purpose it is desirable to prepare a base composition which may be transported to the field in concentrated-form and there diluted with a dispersing or carrying agent, such as water. An example of a suitable base composition or concentrate of this type is as follows:

' Percent by Ingredient weight Cyclopropyl luryl propenone 20-30 Vegetable oil 8-16 Emulsiiler 33 Petroleum spray oil To make 100 be a mixture of higher acids such as is found in the commercial products tall oil, marine fatty acids, coconut fatty acids, and red oil, or it may be a relatively refined product. A suitable petroleum spray oil is the petroleum fraction heretofore described, having a specific gravity of about 0.8018, or a. similar oil blended with a, lesser proportion of heavier neutral oil. Any 011 so used should preferably have a high unsulfonated residue, e. g., 90 or more. This solution is adapted to be used in a 1-400 or 1-800 dilution with water with which it readily emulsifies. This diluted composition may be freely applied to leafy crops and to fruits without danger of phytocidal effect and provides efficient protection against a large number of insect pests.

A simpler but highly effective composition, especially for use in making veterinary dip" solutions, is one in which the principal ingredients are cyclopropyl furyl propenone, about 40% by weight, and polyethylene glycol esters of high er fatty acid. about 60% by weight; Such composition is adapted for use in 1-400 to l-800 dilution in water as an animal wash.

It is frequently desirable to apply insecticides in the form of dust. This is true not only in the case of application to field crops and orchards but also for application to animals. An example of a preparation adapted to be used without further dilution for the dusting. of vegetation is as follows: I

A similar insecticidal dust for application to an 'imals or to living quarters may be made by the use of from 3% to 10% of cyclopropyl furyl propenone in the above formula. An example of wetting agent suitable for use in this formula is sodium lauryl sulfate. Examples of suitable extenders are any one or combination of the following in powdered form: soapstone, talc, pyrophyllite and sulfur. The ingredients of these dust compositions may be ground up together in the desired proportions. One desirable way of preparing such dusts is to dissolve the clyclopropyl furyl ,propenone in a volatile solvent such as a low boiling petroleum fraction or alcohol,

' then to spray this solution over the powdered extender and, after the solvent has been removed by evaporation, to regrind the material.

It has been the practice of contact insecticide comp'ounders to make use of various powdered extenders in addition to those named above. Many of the materials previously used for this purpose have adsorbent properties, for example,

fullers earth, diatomaceous earth, walnut shell flour, etc. While cyclopropyl furyl propenone may be used with such adsorbent materials, we have fouhd that distinctly better results are obtained when it is used in conjunction with non-adsorbent, relatively nonporous materialssuch as those previously mentioned. That is, other things being equal, greater insecticide efficiency is obtained when cyclopropyl furyl propenone is compounded with nonporous dusting powder such as talc, than when it is compounded with adsorbent material such as diatomaceous earth. A preferred form of our invention, therefore, is the use of dusting compositions containing, as the principal toxic ingredient, cyclopropyl fu'ryl propenone together a large number of insects, is not toxic, or not markedly toxic, to all insects, it is in some instances advantageous to incorporate a small amount of one or more of these additional inconcentrations several times those ordinarily needed for adequate pest control, no leaf burning or other injury was observed on this type of plant. Likewise, no apparent harm or appreciable staining was caused by the application of composi .tions containing cyc j insecticidal amounts to fabrics, or i'urnitureflnish. The same freedom from injury ascribable to ity of cyclopropyl iuryl propenone opropyl iuryl propenone in the presence of cyclopropyl furyl propenone is true in the case of oil sprays furyl propenone.

We have previously mentioned the compatibilwith various special-purpose toxicants and carriers. By the term "carrier we intend to include such materials as assist in the dispersionof the cyclopropyl furyl propenone as well as those which impartspreading, wetting, conditioning, adhering. solvent, or emulsifying action. Examples of cai'i'ife'i'sinclude, in addition to those specifically 1 me'ntioned abov chlorinated solvents,v aligvlated' naphthalenes, esters, vegetable oils, and soaps.

- We-claim: I

1 I and .water sprayscontain'ing insecticidal amounts oi cyclopropyl iuryl propenone in oil solution. and a water emulsifying agent. I

6. An insecticidal spray concentrate comprising from 20% to 30% by weight of cyclopropyl Iuryl propenone, from to 20% by weightoi 4 vegetable oil, and the balance consisting oi petroleum spray oil and a water emulsifying agent.

'I. An insecticidal solution in which the principal active ingredients are cyclopropyliuryl pro-- about 1% by weight of a wetting agent, and an inert powdered solid carrier.

3 '1. An insecticidal composition containing as active toxic ingredient cyclopropyl furyl'prope-" noneand a carrier therefor.

2.'-An insecticidal composition containing as active toxic ingredient from 1% to 40% by weight of cyclopropyl furyl propenone and a carrier therefor.

3; An insecticidal composition'containing as active toxic ingredient cyclopropyl furyl propenone in oil solution'and a. carrier thereion 4. .An insectitcidal spray-composition containing as active toxic ingredient from 1% to 5% by weight of cyclopropyl furyl propenone dissolved in plant spray petroleum oil.

5. An insecticidal isng from 20% to 30% by weight of cyclopropyl 10. An insecticidal composition comprising as active toxic ingredient cyclopropyl'iuryl prope-r none extended by means of a. volatile solvent over a powdered solid carrier.

11. An insecticidal composition comprising as active toxic ingredient cyclopropyl iuryl prope none extended by means of a volatile solvent over a nonadsorbent solid carrier.

spray concentrate comprisl 12. The method of controlling insect pests which comprises dispersing over the insect intested area a composition the active toxic ingredient of which is cyclopropyl furyl propenone' together with a carrier therefor.

JAMES w. mans. CARROLL o. oassm 

